Sulfo group-containing disaz compounds having a heterocyclic coupling component radical

ABSTRACT

Disazo compounds of the formula ##STR1## and salt thereof, D is the radical of a diazo component of the benzene or naphthalene series. 
     K is the radical of a heterocyclic coupling component of the aminopyrazole-, pyridone- or barbituric acid-series, n is 1 to 4, 
     R 1  is hydrogen, C 1-4  alkyl or substituted C 1-4  alkyl, 
     each of R 2  and R 3  is independently hydrogen, halo, C 1-4  alkyl, substituted C 1-4  alkyl, C 1-4  alkoxy, substituted C 1-4  alkoxy, --NHCO--Rhd 5, amino, substituted amino or a quaternary ammonium group, wherein R 5  is C 1-4  alkyl, substituted C 1-4  alkyl, C 1-4  alkoxy or amino, 
     R 4  is hydrogen, C 1-4  alkyl, C 1-4  alkoxy, halo or nitro, 
     X is a bridging radical, and with the proviso that the number of anionic groups equals or exceeds the total number of basic and cationic groups, 
     are useful as direct dyes, as such or in the form or solid or particularly liquid aqueous dye preparations, for dyeing or printing hydroxy group- or nitrogen- containing organic substrates, such as textiles consisting of or containing cellulose material, leather, glass and especially paper, and are also useful in inks.

This is a continuation-in-part of application Ser. No. 06/856,606, filedApr. 25, 1986 and now abandoned.

The invention relates to disazo compounds containing sulphonic acidgroups and salts thereof and to a process for their preparation, whichcompounds are suitable for use as direct dyestuffs as such or in theform of dyeing preparations.

According to the invention there is provided compounds of formula I##STR2## and salts thereof, in which D is the radical of a diazocomponent of the benzene or naphthalene series,

X is a bridging group,

K is the radical of a heterocyclic coupling component of theaminopyrazole-, pyridone- or barbituric acid-series,

n is 1, 2, 3 or 4, each of a and b is independently 0 or 1,

R₁ is hydrogen, C₁₋₄ alkyl or substituted C₁₋₄ alkyl, each of R₂ and R₃is independently hydrogen, halogen, C₁₋₄ alkyl, substituted C₁₋₄ alkyl,C₁₋₄ alkoxy, substituted C₁₋₄ alkoxy, --NHCOR₅, amino or a substitutedamino or quaternary ammonium group,

R₄ is hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, halogen or nitro, and

R₅ is C₁₋₄ alkyl, substituted C₁₋₄ alkyl, C₁₋₄ alkoxy or amino, andmixtures of such compounds each of which is in free acid or salt form.

In a compound of formula I n is preferably at least 2. Preferably, Dcontains at least one sulphonic acid group, and additionally to thateach of the rings A and B (provided that a and b, respectively, are 0)and K may also contain a sulphonic acid group. More preferably, Dcontains two or three sulphonic acid groups, most preferably two ofthem.

In a compound of formula I the total number of any basic and/or cationicgroups, e.g. any protonatable amino and/or quaternary ammonium groups,equals or is less than the total number of anionic groups, i.e. thesulpho and carboxy groups present. Depending on the reaction andisolation conditions used for a compound of formula I, the positivecharge of each cationic group is balanced either by the negative chargeof an anionic groups SO₃.sup.⊖ or COO.sup.⊖ or even by O.sup.⊖ formingan internal salt, or by an external anion An.sup.⊖, where An.sup.⊖ is anon-chromophoric anion, such as hydroxide, chloride, bromide, lactate,acetate, propionate, citrate, oxalate, methyl sulphate, ethyl sulphateand hydrogensulphate; most preferably it is a chloride ion.

The term "salt form" encompasses internal and external salt forms aswell as acid addition salt forms.

In the case where a compound of formula I is free of basic and cationicgroups it is in free acid or external salt form. Where it is free ofbasic groups, and the total number of cationic groups (a) equals or (b)is less than the total number of anionic groups, normally an internalsalt is formed, or both groups may be in external salt form, and for (b)the surplus anionic group(s) is (are) in free acid or preferablyexternal salt form. Where it is free of cationic groups, and the totalnumber of basic groups (c) equals or (d) is less than the total numberof anionic groups, normally an internal salt is formed and for (d) thesurplus anionic group(s) is (are) in free acid or preferably externalsalt form, or the anionic groups may be in external salt form, and thebasic group may be in free base or acid addition salt form with an acidHAn, where An.sup.⊖ is a non-chromophoric anion, and the surplus anionicgroup(s) is (are) in external salt form. In principle, the same applieswhere both basic groups and cationic groups are present.

In the specification any halogen means fluorine, chlorine or bromine,especially chlorine.

Generally, any alkyl or akylene is linear or branched unless indicatedto the contrary.

D is preferably Da, where Da is a group of formula (a), (b) or (c),##STR3## in which R₆ is hydrogen or sulpho,

R₇ is hydrogen, halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy or --NHCOC₁₋₄ alkyl,

x is 0 or 1 and

y is 1 or 2.

More preferaby, D is Db, where Db is a group of formula (a₁), (b₁) or(c₁), ##STR4## in which R_(7a) is hydrogen, chlorine, methyl, methoxy oracetamido;

(b₁) is a group of formula (b) in which x+y is 2, the sulpho groups arebound to the 1,5-, 3,6-, 4,8-, 5,7- or 6,8-positions, and when x+y is 3,the sulpho groups are bound to the 3,6,8- or 4,6,8-positions;

(c₁) is a group of formula (c) in which when y is 1, the sulpho groupsare in the 3,6-, 4,6-, 3,8- or 4,8-positions, and when y is 2 the sulphogroups are in the 3,6,8-positions.

Even more preferably, D is Dc, where Dc is a group of formula (a₂) or(b₂), ##STR5## in which R_(7b) is hydrogen, methyl or methoxy;

(b₂) is a group of formula (b) in which x+y is 2 with the sulpho groupsbound to the 4,8- or 6,8-positions.

Particularly preferred as D is Dd, where Dd is a group of formula (b₂)of which a 6,8-disulphonaphthyl-2 group is most preferred.

Preferably, X is Xa, where Xa is --C0--, --CH₂ --, --SO₂ --, --CONR₁ --or ##STR6## in which Y is halogen, hydroxy, amino, C₁₋₄ alkyl, phenoxyor an aliphatic, cycloaliphatic, aromatic or heterocyclic amino group,the latter of which is C- or N-bonded containing 1 to 3 hetero atoms andwhich may be substituted by 1 to 3 C₁₋₄ alkyl groups, any suchsubstituted amino group preferably being C₁₋₂ alkylamino, C₂₋₄hydroxyalkylamino, N,N-di-(C₂₋₄ hydroxyalkyl)amino, --NH--(CH₂)_(m)--SO₃ H, anilino, morpholino, piperidino, piperazino orN-methylpiperazino, wherein m is 2 or 3. Y_(x) is Y wherein anysubstituted amino group has one of these significances. Preferably, Y isY_(a), where Y_(a) is chlorine, hydroxy, methoxy, amino, mono-C₁₋₂alkylamino, monohydroxy-C₂₋₄ alkylamino, di-(hydroxy-C₂₋₄ alkyl)amino,--NH(CH₂)₂₋₃ SO₃ H, anilino, morpholino, piperidino, piperazino orN-methylpiperazino, and R₁ is R_(1a), more preferably R_(1b), whereR_(1a) and R_(1b) are as defined below.

More preferably, X is Xb, where Xb is --CO--, --CH₂ --, --CONR_(1a) --or ##STR7## in which Y_(ax) has one of the significances given for Y_(a)except chlorine.

Even more preferably, X is Xc, where Xc is --CO--, --SO₂ -- or ##STR8##Even more preferably, X is Xd, where Xd is --C0-- or ##STR9## Mostpreferably X is --CO--.

K is preferably Ka, where Ka is a group of formula (d), (e) or (f),##STR10## in which Y₁ is OH or NH₂,

R₈ is C₁₋₄ alkyl, C₁₋₄ alkoxy, NH₂, --CONH₂, --COOR₁, phenyl orsubstituted phenyl,

R₉ is hydrogen, C₁₋₄ alkyl, phenyl or substituted phenyl,

Y₂ is O, S, ═NH, ═N--CN, ═NCONH₂ or ##STR11## Q₁ is hydrogen, CN, NH₂,--NHC₁₋₄ alkyl, OH, C₁₋₄ alkoxy, C₁₋₄ alkyl, C₂₋₄ alkyl monosubstitutedby hydroxy or C₁₋₄ alkoxy, C₅₋₆ cycloalkyl or phenyl or phenyl(C₁₋₄alkyl) which phenyl group of the latter two groups is unsubstituted orsubstituted by one to three groups selected from C₁₋₄ alkyl, C₁₋₄alkoxy, halogen, COOH and SO₃ H; a saturated or unsaturated 5- or6-membered heterocyclic ring containing one to three hetero atoms whichring is unsubstituted or substituted by one to three C₁₋₄ alkyl groupsand which is bound by a carbon or nitrogen atom directly or via a bridgemember provided that any ##STR12## is bound via bridge member; --COR₁₀or --(CH₂)₁₋₃ R₁₁,

R₁₀ is OH, NH₂ or C₁₋₄ alkoxy,

R₁₁ is CN, halogen, SO₃ H, --OSO₃ H, --COR₁₂ or ##STR13## R₁₂ is OH; NH₂; C₁₋₄ alkyl which is unsubstituted or monosubstituted by OH, halogen,CN or C₁₋₄ alkoxy; or phenoxy, phenyl or phenyl(C₁₋₄ alkyl) which phenylgroup of the latter three groups is unsubstituted or substituted by oneto three groups selected from C₁₋₄ alkyl, C₁₋₄ alkoxy, halogen, COOH andSO₃ H;

Q₂ is hydrogen; CN; halogen; SO₃ H; NO; NO₂ ; --NR₁₃ R₁₄ ; C₁₋₄ alkylwhich is unsubstituted or monosubstituted by OH, halogen, CN, C₁₋₄alkoxy, phenyl, SO₃ H or --OSO₃ H; --SO₂ NH₂ ; --COR₁₅ ; --CH₂ NHCOR₁₆E₁ ; a group of the formula ##STR14## in which the carbonyl or sulphonylgroups are bound to two carbon atoms of an aromatic ring which are inortho position to each other; a group containing the moiety ##STR15## inwhich the ammonium ion is part of a 5- or 6-membered ring which containsone to three hetero atoms and which is unsubstituted or substituted byone or two methyl groups by one of the groups NH₂, --NHC₁₋₄ alkyl and--N(C₁₋₄ alkyl)₂ ; or a group of the formula ##STR16## in which R₁₇ ishydrogen or C₁₋₄ alkyl which is unsubstituted or monsubstituted by OH,halogen, CN, C₁₋₄ alkoxy or phenyl,

Z₁ is S, ##STR17## and Z₂ is a group necessary to form a 5- or6-membered ring to which ring a further 5- or 6-membered carbocyclic orheterocyclic ring containing one or two hetero atoms may be condensed,

or

both Q₁ and Q₂ together form a C₃ - or C₄ -chain which may be part of afurther 5- or 6-membered ring by two vicinal chain members,

each of R₁₃ and R₁₄ is independently hydrogen, C₁₋₄ alkyl which isunsubstituted or monosubstituted by OH, halogen, CN, C₁₋₄ alkoxy orphenyl; or --COR₁₆ E₁,

R₁₅ is OH, NH₂, --NHC₁₋₄ alkyl, --N(C₁₋₄ alkyl)₂, C₁₋₄ alkyl, C₁₋₄alkoxy, phenyl or phenoxy which phenyl group of the latter two groups isunsubstituted or substituted by one to three groups selected from C₁₋₄alkyl, C₁₋₄ alkoxy, halogen, COOH and SO₃ H,

R₁₆ is C₁₋₆ alkylene,

E₁ is hydrogen, halogen, a protonatable amino group, a quaternaryammonium group or a hydrazinium group, SO₃ H or --OSO₃ H;

Q₃ is hydrogen; --NR₁₈ R₁₉ ; a saturated or unsaturated 5- or 6-memberedheterocyclic ring containing one or two hetero atoms which is bound by acarbon or nitrogen atom and which is unsubstituted or substituted by upto three methyl groups or by one of the groups NH₂, --NHC₁₋₄ alkyl and--N(C₁₋₄ alkyl)₂ ; C₁₋₆ alkyl; C₂₋₄ alkenyl; C₂₋₄ alkynyl; C₁₋₆ alkylmonosubstituted by OH, CN, C₁₋₄ alkoxy, acetamido, --COR₂₀, SO₃ H or--OSO₃ H; C₅₋₆ cycloalkyl; phenyl or phenyl(C₁₋₄ alkyl) which phenylgroup of the latter two groups is unsubstituted or substituted by one tothree groups selected from C₁₋₄ alkyl, C₁₋₄ alkoxy, halogen, NO₂, NH₂,COOH and SO₃ H; --C₁₋₆ alkylene-E₂, ##STR18## each of R₁₈ and R₁₉ isindependently hydrogen, C₁₋₄ alkyl, C₁₋₄ alkyl monosubstituted by OH,halogen, CN or C₁₋₄ alkoxy; phenyl or phenyl substituted by one or twogroups selected from halogen, C₁₋₄ alkyl and C₁₋₄ alkoxy,

R₂₀ is OH or C₁₋₄ alkoxy,

E₂ is a protonatable amino group, a quaternary ammonium group, ahydrazinium group or a group ##STR19## R₂₁ is E₃, --NHCOR₁₆ E₃, --SO₂NHR₁₆ E₃ or --CONHR₁₆ E₃,

each R₂₂ is independently halogen, NH₂ or an aliphatic amino group, and

E₃ is a protonatable amino group, a quaternary ammonium group or ahydrazinium group; and

Q₄ is hydrogen or OH with the proviso that Q₄ is hydrogen when Q₁ is OH.

Any substituted C₁₋₄ alkyl as R₁ is preferably C₁₋₄ alkylmonosubstituted by hydroxy, chloro, cyano, carboxy or sulpho.Accordingly, R₁ is, for example, R_(1x), where R_(1x) is hydrogen, C₁₋₄alkyl or C₁₋₄ alkyl monosubstituted by hydroxy, chloro, cyano, carboxyor sulpho.

R₁ is preferably R_(1a), where R_(1a) is hydrogen, methyl, ethyl or C₁₋₃alkyl monosubstituted by hydroxy, chlorine, cyano, carboxy or sulpho.More preferably, it is R_(1b), where R_(1b) is hydrogen, methyl orethyl; most preferably, R₁ is hydrogen.

Y₁ is preferably OH.

R₈ is preferably R_(8a), where R_(8a) is methyl, methoxy, --CONH₂,--COOH, --COOC₁₋₂ alkyl or phenyl. More preferably R₈ is R_(8b), whereR_(8b) is methyl, --COOH or --CONH₂ ; most preferably R₈ is methyl.

R₉ is preferably R_(9a), where R_(9a) is hydrogen, methyl, phenyl orphenyl substituted by one or two groups selected from C₁₋₄ alkyl, C₁₋₄alkoxy, chlorine, acetamido, --NHCOR₁₆ B₂, --SO₂ NHR₁₆ B₂ (which B₂ inthe latter two groups is as defined below), carboxy and sulpho. Morepreferably, R₉ is R_(9b), where R_(9b) is phenyl or phenyl substitutedby one or two groups selected from methyl, methoxy, chlorine and sulpho.

The group (d) is preferably (d₁) of the formula ##STR20## especially(d₂) of the formula ##STR21## The group (e) is preferably (e₁) of theformula, ##STR22## in which Y_(2a) is O, S, ═NH, ═HCH or ═NCONH₂ ;especially (e₂) of the formula, ##STR23## in which Y_(2b) is ═NCN or═NCONH₂.

Any alkyl or alkoxy as Q₁ preferably contains 1 or 2 carbon atoms and ismost preferably methyl or methoxy. Any substituted alkyl is preferably aC₂₋₃ alkyl group monosubstituted by hydroxy or C₁₋₂ alkoxy. Anycycloalkyl is preferably cyclohexyl.

Preferably, in any substituted phenyl or phenylalkyl group the phenylgroup contains one or two groups selected from methyl, methoxy,chlorine, --COOH and --SO₃ H.

Any heterocyclic ring as Q₁ is preferably morpholine, pyrrolidine,piperidine, piperazine or N-methylpiperazine (when saturated) which isbound by a carbon or nitrogen atom, or is pyridine, triazine,pyridazine, pyrimidine or pyrazine (when unsaturated) which is bound bya carbon or nitrogen atom where in the latter case (when bound by anitrogen atom) a methylene bridge is present.

R₁₀ is preferably R_(10a), where R_(10a) is OH, NH₂, methoxy or ethoxy.More preferably it is R_(10b), where R_(10b) is OH or NH₂.

R₁₂ is preferably R_(12a), where R_(12a) is OH, NH₂, methyl, ethyl,methoxy or ethoxy. More preferably it is R_(12b), where R_(12b) is OH orNH₂.

R₁₁ is preferably R_(11a), where R_(11a) is CN, chlorine, SO₃ H, --OSO₃H, ##STR24## or --COR_(12a). More preferably it is R_(11b), whereR_(11b) is SO₃ H, --OSO₃ H, ##STR25## or --COR_(12b).

Q₁ is preferably Q_(1a), where Q_(1a) is hydrogen, CN, NH₂, OH, methyl,ethyl, 2-hydroxyethyl, 2-C₁₋₂ alkoxyethyl, methoxy, ethoxy, cyclohexyl;phenyl or phenyl-C₁₋₂ alkyl which phenyl group of the latter two groupsis unsubstituted or substituted by one or two groups selected frommethyl, methoxy, chlorine, COOH and SO₃ H; ##STR26## More preferably Q₁is Q_(1b), where Q_(1b) is NH₂, methyl, ethyl, 2-hydroxyethyl,cyclohexyl, phenyl, phenyl-C₁₋₂ alkyl, --COR_(10b) or --CH₂ R_(11b).Even more preferably Q₁ is Q_(1c), where Q_(1c) is NH₂, methyl, phenyl,phenylethyl or --CH₂ SO₃ H. Most preferably Q₁ is methyl.

Any protonatable amino or quaternary ammonium group as E₁, E₂ or E₃ ispreferably a group B₁, where B₁ is a primary amino group, a secondary ortertiary aliphatic, cycloaliphatic, aromatic or saturated, unsaturatedor partially unsaturated heterocyclic amino group which latter group isattached by the N-atom or a carbon atom; or a quaternary ammonium groupcorresponding to the above.

Any aliphatic amino group as B₁ is preferably a mono-C₁₋₄ -alkyl- or adi-(C₁₋₄ alkyl)-amino group. The alkyl group may be monosubstituted byhalogen, hydroxy, cyano, C₁₋₄ alkoxy or phenyl. Any cycloaliphatic aminogroups is preferably C₅₋₆ cycloalkylamino, the cycloalkyl group of whichis unsubstituted or may be substituted by one or two C₁₋₂ alkyl groups.

Any aromatic amino group is preferably phenylamino, the phenyl ring ofwhich is unsubstituted or substituted by one or two groups selected fromhalogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, SO₃ H and COOH.

Any heterocyclic amino groups as B₁ which is attached by the N-atom or acarbon atom is preferably a saturated, unsaturated or partiallyunsaturated 5- or 6-membered ring which contains one or two hetero atomsand may be substituted by one or two C₁₋₄ alkyl groups.

B₁ is more preferably a group B₂, where B₂ is a protonatable amino group--NR₂₃ R₂₄ or a quaternary ammonium group --N.sup.⊕ R₂₅ R₂₆ R₂₇, each ofR₂₃ and R₂₄, independently, is hydrogen, C₁₋₂ alkyl, unbranchedhydroxy-C₂₋₃ alkyl or benzyl or both R₂₃ and R₂₄, together with theN-atom to which they are attached, form a pyrrolidine, piperidine,morpholine, piperazine or N-methylpiperazine group,

each of R₂₅ and R₂₆ has independently one of the non-cyclic or cyclicsignificances of R₂₃ and R₂₄ except hydrogen, and

R₂₇ is methyl, ethyl or benzyl, or

R₂₅, R₂₆ and R₂₇, together with the N-atom to which they are attached,form a pyridinium group unsubstituted or substituted by one or twomethyl groups.

Most preferably B₁ is B₃, where B₃ is --NR_(23a) R_(24a) or --N.sup.⊕R_(25a) R_(26a) R_(27a),

each of R_(23a) and R_(24a) is hydrogen, methyl or ethyl, or bothR_(23a) and R_(24a), together with the N-atom to which they are attachedform a piperidine, morpholine, piperazine or N-methylpiperazine ring;

each of R_(25a) and R_(26a) is methyl or ethyl or both R_(25a) andR_(26a), together with the N-atom to which they are attached, has one ofthe cyclic significances of R_(23a) and R_(24a),

R_(27a) is methyl or ethyl or

R_(25a), R_(26a) and R_(27a), together with the N-atom to which they areattached, form a pyridinium group unsubstituted or substituted by one ortwo methyl groups.

E₁ is preferably E_(1a), where E_(1a) is hydrogen, chlorine, a group B₂or SO₃ H. More prefrerably it is E_(1b), where E_(1b) is hydrogen,chlorine, a group B₃ or SO₃ H.

R₁₃ and R₁₄ are preferably R_(13a) and R_(14a), where each of R_(13a)and R_(14a) is independently hydrogen, C₁₋₂ alkyl, C₁₋₂ alkylmonosubstituted by OH, C₁₋₂ alkoxy or phenyl, or --COR_(16a) E_(1a), inwhich R_(16a) is C₁₋₂ alkylene. More preferably R₁₃ and R₁₄ are R_(13b)and R_(14b), where each of R_(13b) and R_(14b) is independentlyhydrogen, methyl or --COR_(16a) E_(1b).

R₁₅ is preferably R_(15a), where R_(15a) is OH, NH₂, --NHCH₃, --N(CH₃)₂,methyl, ethyl, methoxy or ethoxy. More preferably it is R_(15b), whereR_(15b) is NH₂, methyl, ethyl, methoxy or ethoxy.

Q₂ is preferably Q_(2a), where Q_(2a) is hydrogen, CN, chlorine, SO₃ H,--NR_(13b) R_(14b), methyl, ethyl, C₁₋₂ alkyl monosubstituted by OH,phenyl, SO₃ H or --OSO₃ H; --COR_(15a), --CH₂ NHCOR_(16a) E_(1b) or agroup which contains the moiety ##STR27## forming a pyridine, pyrimidineor benzimidazole ring which is unsubstituted or monosubstituted bymethyl, NH₂, --NHCH₃ or --N(CH₃)₂. More preferably it is Q_(2b), whereQ_(2b) is hydrogen, CN, chlorine, --NHR_(13b), --CH₂ SO₃ H, --COR_(15b),--CH₂ NHCOCH₂ E_(1b), ##STR28##

Even more preferably Q₂ is Q_(2c), where Q_(2c) is hydrogen, CN,chlorine, --CONH₂, ##STR29## Most preferably Q₂ is hydrogen.

It is also preferred that Q₁ and Q₂ as Q_(1a) and Q_(2a) together withthe carbon atoms to which they are attached form part of a further ringwhich corresponds to the formula ##STR30## for example, they form a ringof the formula ##STR31## in which Y₃ is --(CH₂)₁₋₂ --, ##STR32## and theasterisked carbon atom is bound to the methylene group in the Q₁-position.

R₁₈ and R₁₉ are preferably R_(18a) and R_(19a), where each of R_(18a)and R_(19a) is independently hydrogen, methyl, ethyl or phenyl.

R₂₀ is preferably R_(20a), where R_(20a) is OH, methoxy or ethoxy.

Any aliphatic amino group as R₂₂ is preferably a mono-C₁₋₄ alkyl- ordi-(C₁₋₄ alkyl)-amino group, in which the alkyl groups may bemonosubstituted by halogen, OH, CN, C₁₋₄ alkoxy or phenyl.

Each R₂₂ is preferably R_(22a), where each R_(22a) is independentlychlorine, NH₂, --NHC₁₋₂ alkyl or --N(C₁₋₂ alkyl)₂, in which the alkylgroups are unsubstituted or monosubstituted by OH, CN or C₁₋₂ alkoxy.More preferably each R₂₂ is R_(22b), where R_(22b) is independentlychlorine, NH₂, --NHCH₃, --N(CH₃)₂, --NHCH₂ CH₂ OH or --N(CH₂ CH₂ OH)₂.

E₂ is preferably E_(2a), where E_(2a) is a group B₂ or a group of theformula ##STR33## More preferably it is E_(2b), where E_(2b) is a groupB₃ or a group of the formula ##STR34##

E₃ is preferably E_(3a), where E_(3a) is a group B₂ ; more preferably itis E_(3b), where E_(3b) is a group B₃.

R₂₁ is preferably R_(21a), where R_(21a) is E_(3a), --NHCOR_(16a)E_(3a), --SO₂ NHR_(16a) E_(3a) or --CONHR_(16a) E_(3a). More preferablyit is R_(21b), where R_(21b) is E_(3b), --NHCOCH₂ E_(3b) or --CONHCH₂E_(3b).

Q₃ is preferably Q_(3a), where Q_(3a) is hydrogen; --NR_(18a) R_(19a) ;phenyl; phenyl--C₁₋₂ alkyl; cyclohexyl; C₁₋₄ alkyl; C₁₋₄ alkylmono-substituted by OH, CN, C₁₋₂ alkoxy, --COR_(20a), SO₃ H or --OSO₃ H;--C₁₋₃ alkylene-E_(2a) ; ##STR35## More preferably it is Q_(3b), whereQ_(3b) is hydrogen, --NHR_(18a), phenyl- --C₁₋₂ alkyl; methyl; ethyl;C₁₋₂ alkyl monosubstituted by OH, SO₃ H or COR_(20a) ; --(CH₂)₁₋₃-E_(2b) ; ##STR36## Most preferably Q₃ is hydrogen.

The group (f) is preferably (f₁) of the formula ##STR37## with theproviso that Q₄ is hydrogen when Q_(1a) is OH; more preferably (f₂) ofthe formula ##STR38## even more preferably (f₃) of the formula ##STR39##most preferably (f₄) of the formula ##STR40## in which Q_(2c) beinghydrogen is especially preferred.

More preferably, K is Kb, where Kb is a group (d₁), (e₁) or (f₁); evenmore preferably it is Kc, where Kc is a group (d₂), (e₁) or (f₂); evenmore preferably it is Kd, where Kd is a group (e₁) or (f₃); even morepreferably, K is Ke, where Ke is a group (e₂) or (f₄) in which Q_(2c)being hydrogen is especially preferred; most preferably, K is Kf, whereKf is a group (e₂).

In the ring A, R₂ and R₃ are preferably in para-position to each otheraccording to the formula ##STR41## in which, preferably, R₂ is R_(2b)and R₃ is R_(3a), where R_(2b) and R_(3a) are as defined below.

Any halogen as R₂ or R₃ is preferably chlorine; any alkyl or alkoxy ispreferably methyl or methoxy. Any substituted alkyl group as R₂ or R₃ ispreferably C₁₋₄ alkyl monosubstituted by SO₃ H; or a group --(CH₂)₁₋₃--E_(3b). Any substituted alkoxy is preferably monosubstituted by SO₃ H.Any substituted amino or quaternary ammonium group as R₂ or R₃ ispreferably a group E_(3b), more preferably a quaternary ammonium group.

Any substituted alkyl as R₅ is preferably a group --S(CH₂)₁₋₃ --E_(3b).Accordingly, R₅ is, for example, R_(5x), where R_(5x) is C₁₋₄ -alkyl,--(CH₂)_(t) --NR_(23a) R_(24a), --(CH₂)_(t) --N.sup.⊕ R_(25a) R_(26a)R_(27a), C₁₋₄ alkoxy or amino, wherein t is 1, 2 or 3.

R₅ is preferably R_(5a), where R_(5a) is methyl, methoxy, NH₂ or--(CH₂)₁₋₃ --E_(3b). More preferably it is R_(5b), where R_(5b) ismethyl or NH₂. Accordingly, Ring A is preferably substituted by oneR_(2x) and one R_(3x), where each of R_(2x) and R_(3x) is independentlyhydrogen, halo, C₁₋₄ alkyl, sulpho(C₁₋₄ alkyl), --(CH₂)_(t) --NR_(23a)R_(24a), --(CH₂)_(t) --N.sup.⊕ R_(25a) R_(26a) R_(27a), C₁₋₄ alkoxy,sulpho(C₁₋₄ alkoxy), --NH--CO--R_(5x), --NR_(23a) R_(24a), --N.sup.⊕R_(25a) R_(26a) R_(27a) or sulpho, with the proviso that R_(2x) is otherthan sulpho.

R₂ is prefetably R_(2a), where R_(2a) is hydrogen, chlorine, methyl,methoxy, --NHCOR_(5a), --(CH₂)₁₋₃ --SO₃ H, --O(CH₂)₃ --sO₃ H or--(CH₂)₁₋₃ --E_(3b). More preferably it is R_(2b), where R_(2b) ishydrogen, methyl, methoxy, --NHCOCH₃ or --NHCONH₂ ; most preferably itis R_(2c), where R_(2c) is hydrogen or methyl.

R₃ is preferably R_(3a), where R_(3a) is hydrogen, methyl or methoxy.

Ring B is preferably substituted by one R_(4x), where R_(4x) ishydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, halo, nitro or sulpho.

R₄ is preferably R_(4a), where R_(4a) is hydrogen, C₁₋₂ alkyl or C₁₋₂alkoxy; especially R₄ is hydrogen.

Preferably, the azo group bound to the ring B is in meta- orpara-position with respect to the carbon atom linked to X; morepreferably it is in the para-position.

Representative compounds of formula I are those of formula Ix ##STR42##and salts thereof, wherein Kb₁ is a group of formula (e₁) or (f₁), andany Y in Xa is Y_(x), with the provisos that each compound contains 1,2, 3 or 4 sulpho groups, and the number of sulpho groups equals orexceeds the total number of basic and cationic groups, and mixtures ofsuch compounds each of which is in free acid or salt form.

Preferred compounds and salts of formula Ix are those

(i) wherein the Kb₁ --N═N-- group is in the 3- or 4-position of Ring B,

(ii) wherein R_(1x) --R_(3x) are R_(1a) --R_(3a), respectively, andY_(x) is Y_(a),

(iii) of (ii) wherein R_(2x) is in the 6-position of Ring A, and R_(3x)is in the 3-position of Ring A,

(iv) of (ii) wherein R_(2x) is R_(2b),

(v) of (iv) wherein the Kb₁ --N═N-- group is in the 3- or 4-position ofRing B,

(vi) of (v) wherein Kb₁ is a group of formula (e₁),

(vii) of (v) wherein Kb₁ is a group of formula (f₁), and (viii) of (i)wherein Xa is Xb.

More preferred compounds and salts of formula Ix are those of formulaIxa ##STR43## wherein R_(4ax) is as defined below, and the Kb₁ --N═N--group is in the 3- or 4-position of Ring B.

Preferred compounds and salts of formula Ixa are those

(i) wherein Xc is Xd,

(ii) wherein Da is Db,

(iii) wherein R_(1b) is hydrogen,

(iv) wherein R_(4ax) is hydrogen,

(v) wherein Xc is --CO--,

(vi) wherein the Kb₁ --N═N-- group is in the 4-position of Ring B,

(vii) of (vi) wherein R_(1b) is hydrogen, R_(4ax) is hydrogen, and Xc is--CO--, and

(viii) of (vii) wherein Kb₁ is a group of formula (e₂).

Preferred compounds of formula I include those wherein

(1) D is Da, and X is Xb, and

(2) D is Dc, K is Ka, and X is Xd.

Preferred compounds correspond to formula Ia, ##STR44## any R₁ is R_(1x)and any Y in which the azo group is bound to the 3- or 4-position andR_(4ax) is hydrogen, C₁₋₂ alkyl, C₁₋₂ alkoxy or SO₃ H.

More preferably, in a compound of formula Ia

(1) Da is Db;

(2) R_(1b) is hydrogen;

(3) R_(4ax) is hydrogen;

(4) Xb is Xd;

(5) the azo group is bound to the 4-position.

More preferred compounds correspond to formula Ib, ##STR45## in whichthe azo group is bound to the 3- or 4-position.

Even more preferred are compounds of formula Ib, in which

(1) Db is Dc;

(2) Db is Dd;

(3) Kd is Ke;

(4) those of (1) to (3) in which the azo group is bound to the4-position;

(5) those of (4) in which R_(2b) is R_(2c) ;

(6) those of (1) to (5) in which Kd is Kf.

A compound of formula I according to the invention is preferably in freeacid form, in alkali metal or unsubstituted or substituted ammonium saltform or in mixed salt form, or may form an internal salt. Anysubstituted ammonium cation may be derived from a primary, secondary ortertiary amine. For example, the following amines are suitable:- mono-,di- or tri-methyl-, -ethyl-, -propyl- or -butyl-amine; mono-, di- ortri-ethanol-, -propanol- or -isopropanol-amine;N-methyl-N-hydroxyethylamine, N-methyl-N,N-di(hydroxyethyl)amine,N-ethyl-N-hydroxyethoxyethylamine, morpholine, piperidine, piperazine,hydroxyethylmorpholine, hydroxyethylpiperazine, aminoethylpiperazine;ethylenediamine, hexamethylenediamine; dimethylaminopropylamine,diethylaminopropylamine, diethylene glycol amine, diglycol amine and3-methoxypropylamine.

Also suitable as amines are polyglycol amines. They can be prepared, forexample, by reacting ammonia, alkyl- or hydroxyalkylamine with alkyleneoxides.

Any substituted ammonium ion may also be a quaternary ammonium ionderived from ammonium compounds which preferably contain one or twoquaternary ammonium ions. Examples are tetramethyl-, tetraethyl-,trimethylethyl-, dimethyl-di(2-hydroxypropyl)-, trimethylhydroxyethyl,tetrahydroxyethyl- and trimethylbenzylammonium hydroxide.

The compounds of formula I and mixtures thereof may be prepared byreacting the diazonium salt of one or more aminoazo compounds of formulaII ##STR46## with a compound of formula III ##STR47## or a mixture ofcompounds of formula III, in which the symbols are as defined above andp is 1, 2, 3 or 4, q is 0, 1, 2 or 3 and p+q is 1, 2, 3 or 4.

The starting compounds of formula II are either known or may be preparedin accordance with known methods from known starting compounds.

Similarly, the coupling components of formula III are either known ormay be prepared in accordance with known methods using known startingmaterials. For example, coupling components of the pyridone seriescorresponding to formula IIIa ##STR48## in which Q_(3x) is --C₁₋₆alkylene-E₂ or the group ##STR49## may be prepared by reacting acompound of formula IIIb, ##STR50## in which W is C₁₋₆ alkylene or agroup ##STR51## R₂₈ is --NHCOR₁₆ --, --SO₂ NHR₁₆ -- or --CONHR₁₆ --, andX_(o) is a functional group, preferably a group capable of being splitoff as an anion, with an amino compound E₂ --H.

Diazotisation and coupling reacitons may be effected in accordance withknown methods.

Diazotisation conveniently is carried out in a medium containing amineral acid, preferably hydrochloric acid, at 0°-20° C. Couplingconveniently is carried out at pH 3-10, preferably 4-8.

The resulting compound of formula I may be used in the form of thesolution as obtained; however, this solution may also be converted intoa solid by spray-drying. Furthermore, the conventional method ofisolation used for dyestuffs, salting out of the solution, filtering offand drying, is also suitable.

The type of cations present in a compound of formula I may be influencedin different ways depending on the preparation process. One possibilityconsists in filtering off the diazonium salt which is obtained in theabove process, and washing it with water. The solid diazonium compoundis then added to an aqueous slurry or solution of the couplingcomponent, which contains a basic salt, lithium-, sodium-, potassium-,ammonium-hydroxide, one or more organic amines or a quaternary ammoniumcompound. Another method consists in converting the compound of formulaI, which is obtained by diazotisation and coupling and is isolated insodium salt form, into the free acid by using a mineral acid, preferablyhydrochloric acid, then filtering and washing with water; the compoundis subsequently neutralised and thus converted into the desired alkalimetal salt or ammonium salt. Any type of mixed salt form may be obtainedby effecting partial conversion into the free acid and/or by step-wiseneutralisation.

The salt-changing method, conversion of one salt form into another, canalso be used.

If diazotisation takes place using alkyl nitrites, dinitrogen trioxideor mixtures of nitric oxide and oxygen instead of alkali metal nitrite,it is possible to produce solutions of the end products which are freefrom metal ions. If desired, corresponding salts may be obtained byadding a base which yields cations or by adding an amine.

The compounds according to the invention in form of their water-solublesalts are useful for dyeing or printing hydroxy group- ornitrogen-containing organic substrates. For example, they are suitablefor dyeing or printing fibres, threads or textiles produced therefrom,which consist of or contain cellulose materials, such as cotton, inaccordance with known methods; cotton is preferably dyed by the exhaustmethod, for example from a long or short liquor, at room temperature toboiling temperatures. Printing is effected by means of impregnation witha printing paste which is prepared by known methods.

The new dyestuffs can also be used for dyeing or printing leather,preferably chrometanned types of leather, as well as glass or glassproducts consisting of variable chemical components in accordance withknown methods. Furthermore, the dyestuffs are suitable for thepreparation of inks in accordance with conventional methods.

The compounds of formula I are especially suited for dyeing or printingpaper in accordance with known methods, e.g. for the preparation ofsized or unsized paper dyed in the stock. They may also be used fordyeing paper by the dipping process.

The dyeings and prints obtained (especially those on paper) have goodfastness to usage.

The compounds of formula I may be used as such or may also be used inthe form of dyeing preparations, which are preferably used for dyeingpaper. Suitable liquid, preferably aqueous, concentrated dyeingpreparations may be made in accordance with known methods,advantageously by dissolving in suitable solvents, optionally adding anadjuvant, e.g. a hydrotropic compound or a stabiliser. The possibilityof producing such stable, aqueous concentrated preparations in thecourse of dyestuff synthesis without intermediate isolation of thedyestuff is particularly advantageous. In this process, coupling takesplace for example in the presence of appropriate amines and inparticular in the presence of quaternary ammonium hydroxides which serveto introduce corresponding cations as defined above, and optionally inthe presence of further hydrotropic adjuvants.

Suitable hydrotropic adjuvants are for example low molecular weightamides, lactones, alcohols, glycols or polyols, low molecular weightethers or hydroxyalkylation products, as well as nitriles or esters;among these the following compounds are preferably used: - Methanol,ethanol, propanol; ethylene-, propylene-, diethylene-, thiodiethylene-and dipropylene-glycol; butanediol; β-hydroxypropionitrile,pentamethylene glycol, ethylene glycol monoethyl- and -propylether,ethylene diglycol monoethylether, triethylene glycol monobutylether,butyl polyglycol, formamide, dimethylformamide, pyrrolidone,N-methylpyrrolidone, glycol acetate, butyrolactone, urea andε-caprolactam.

Hydrotropic compounds are described e.g. by H. Rath and S. Muller, inMelliand Textilberichte 40, 787 (1959) or by E. H. Daruwalla in K.Venkataraman, The Chemistry of synthetic Dyes, Vol. VIII, pages 86-92(1974).

The additional content of a hydrotropic compound further improves thestability on storage of the dyestuff preparation, and the solubility ofthe dyestuff employed.

An example of a suitable liquid dye preparation is (all parts are byweight):

100 parts of a compound of formula I in water-soluble salt form,

1-100, preferably 1-10, parts of an inorganic salt,

100-800 parts of water,

0-500 parts of one of the hydrotropic compounds mentioned above.

Depending on the salt form used, the liquid dye preparation may be asuspension but is preferably a true solution. The preparations arestable and can be stored for a long period of time.

Similarly, the compounds of formula I may be made into solid, preferablygranulated dyeing preparations in accordance with known methods,advantageously by granulating as described in French PatentSpecification No. 1.581.900.

A suitable granulate preparation comprises (all parts are by weight):

100 parts of a compound of formula I in water-soluble salt form,

1-100, preferably 1-10, parts of an inorganic salt,

0-800 parts of a standardising agent (preferably non-ionic, such asstarch, dextrin, sugar, glucose and urea).

The solid preparation may contain up to 10% residual moisture.

Depending on the cation or cation mixture present, the dyestuffs offormula I possess good solubility properties, particularly goodsolubility in cold water. Furthermore, when used in paper-making, theycolour the waste water only to a slight extent or not at all. They donot mottle on paper and are substantially insensitive to fillingmaterial and pH over wide ranges. They are only slightly inclined togive two-sided dyeing on paper. The dyeings on paper have good lightfastness properties; after a long-term exposure to light, the shadealters tone-in-tone. The dyed papers also have very good wet fastnessproperties, they are fast not only to water, but also to milk, fruitjuices, sweetened mineral water and tonic water, and in addition theyshow good alcohol fastness properties.

The dyestuffs have good substantivity, i.e. they exhaust practicallyquantitatively, and show good built-up; they can be added to the paperpulp directly, i.e. without previously dissolving, as a dry powder orgranulate, without reducing the brilliance or the yield of colour. It isadvantageous to use the genuine solutions of the dyestuffs as givenabove, which are stable, of low viscosity and thus capable of beingaccurately measured out. Fibre materials which contain mechanical woodpulp are dyed in good, even quality with the dyestuffs of the presentinvention. The dyed paper is both oxidatively and reductivelybleachable, which is important for the recycling of waste paper.

The following examples further serve to illustrate the invention. In theexamples, all parts and percentages are by weight or volume unlessotherwise stated, and the temperatures are in degrees centigrade.

EXAMPLE 1

40.7 Parts of the aminoazo dyestuff prepared by the weakly acid couplingof diazotised 2-aminonaphthalene-6,8-disulphonic acid withaniline-ω-methanesulphonic acid and subsequent saponification in analkaline medium, are stirred into 500 parts of water. The pH is adjustedto 6.5 by the addition of a small amount of acetic acid. The mixture isheated to 50°, then 20 parts of 4-nitrobenzoyl chloride dissolved in 200parts of acetone are added dropwise. Simultaneously, sodium carbonate isadded to keep the pH at 6-7. Stirring is effected for a further threehours, then the pH of the reaction mixture is adjusted to 9 by theaddition of sodium hydroxide solution. The dyestuff intermediate whichprecipitates is filtered.

The resulting presscake is stirred into 500 parts of water. A paleyellow suspension is formed to which 40 parts of crystalline sodiumsulphide are added. After stirring for two hours the reduction iscompleted, and a brownish suspension is obtained. By heating to 90° asolution is formed to which 50 parts of sodium chloride are added. Themixture is cooled to room temperature whilst stirring. The dyestuffwhich precipitates is filtered, washed with brine and dried. Theaminoazo compound corresponding to the formula ##STR52## is obtained.

10.5 Parts of this compound are dissolved in 100 parts of water, and 1.5parts of sodium nitrite are added. This mixture is poured into apreparation of 200 parts of ice and 10 parts of 30% hydrochloric acid. Adark viscous diazo suspension is obtained which is stirred for threehours at 0°-5°. Any excess nitrous acid is decomposed by adding one partof sulphamic acid. Subsequently, 3 parts of4-methyl-6-hydroxypyridone-(2) are added to the diazo suspension. The pHis elevated to 7-8 by adding 30% sodium hydroxide solution, wherebycoupling commences. After about two hours coupling is completed. Theprecipitated product is filtered, washed with brine and dried. Thedyestuff corresponding to the formula ##STR53## is obtained which dyespaper a neutral-yellow shade. The resulting paper dyeings have notablygood wet and light fastness properties.

EXAMPLE 2

43.7 Parts of the aminoazo dyestuff prepared by weakly acid coupling ofdiazotised 2-aminonaphthalene-6,8-disulphonic acid (30.5 parts) with 22parts of o-anisidine-ω-methanesulphonic acid and subsequentsaponification in an alkaline medium, are stirred into 400 parts waterof 80°. Within two hours 24 parts of 4-nitrobenzoyl chloride are addedin small portions. Simultaneously, the pH is kept at 6-7 by the dropwiseaddition of sodium hydroxide solution. When the last portion of4-nitrobenzoyl chloride has been added, stirring is effected for afurther three hours. The dyestuff intermediate which precipitates almostquantitatively is filtered and thoroughly washed with brine.

The resulting presscake is stirred into 400 parts of water and heated to50°. Then 35 parts of crystalline sodium sulphide are added portionwise.Due to the exothermic evolution of heat the temperature of the reactionmixture increases to 65°. By adding 75 parts of sodium chloride thedyestuff precipitates completely. It is filtered with suction,thoroughly washed with brine and dried. The aminoazo compoundcorresponding to the formula ##STR54## is obtained.

55.6 Parts of this compound are dissolved in 800 parts of water, and 27parts of a 4N sodium nitrite solution are added. This mixture is droppedinto a preparation consisting of 200 parts of ice, 50 parts of 30%hydrochloric acid and 150 parts of sodium chloride. A dark diazosuspension is obtained which is stirred for a further one hour. Anyexcess nitrous acid is decomposed by adding one part of sulphamic acid.Subsequently, 16 parts of 2-cyanimino-4,6-dihydroxypyrimidine are addedto the diazo suspension. The pH is elevated to 7-8 by adding 30% sodiumhydroxide solution. After about two hours coupling is completed. Theprecipitated product is filtered, washed with brine and dried. Thedyestuff corresponding to the formula ##STR55## is obtained showing ahigh colouring strength. It dyes paper a brilliant neutral-yellow shade.The resulting paper dyeings have notably good wet and light fastnessproperties.

EXAMPLE 3

When according to the method described in Example 2, 19 parts ofaniline-ω-methanesulphonic acid are used instead of 22 parts ofo-anisidine-ω-methanesulphonic acid the dyestuff corresponding to theformula ##STR56## is obtained which dyes paper a brilliantgreenish-yellow shade. The dyeings show good light and wet fastnessproperties.

EXAMPLES 4 TO 112/Table 1

By a method analogous to that of any one of Examples 1 to 3 furthercompounds of formula I may be prepared using appropriate startingcompounds. They correspond to formula (A), ##STR57## in which thesymbols are defined in Table 1 below. These dyestuffs dye paper agreenish-yellow to reddish-yellow shade; the thus obtained dyeings showgood light and wet fastness properties.

In particular, the shade on paper obtained with the dyestuffs of Table 1is as follows:

(a) reddish-yellow: for Examples 7, 9, 11, 20, 26, 33, 42-47, 50-60,63-66, 73, 75, 100, 105 and 107;

(b) golden-yellow: for Examples 6, 17, 19, 30, 34, 35, 41, 49, 69, 71,80, 84, 91, 96 and 104;

(c) neutral-yellow: for Examples 4, 5, 8, 10, 12-16, 18, 21-25, 27-29,31, 32, 36-40, 48, 61, 62, 67, 68, 70, 72, 74, 76-79, 81-83, 85-90,92-95, 97-99, 101, 102, 106, 108, 109 and 112;

(d) greenish-yellow: for Examples 103, 110 and 111.

The positive charge of each cationic group present in a compound listedin the following Tables 1, 3 and 4 is balanced by the negative charge ofan SO₃.sup.⊖ ion or by An.sup.⊖, where An.sup.⊖ is a non-chromophoricanion, e.g., an anion of the reaction medium, preferably a chloride,acetate or hydroxide ion. Each protonatable amino group present forms aninternal salt with a sulpho group. Where no cationic or protonatableamino group is present or where the total number of anionic groups aregreater than the total number of cationic or basic groups, the anionicgroup(s) is (are) in external salt form, especially in the sodium saltform.

                                      TABLE 1                                     __________________________________________________________________________    Compounds of formula (A)                                                      Ex. No.                                                                            D                 R.sub.2                                                                             R.sub.3x                                                                          K                                            __________________________________________________________________________     4                                                                                  ##STR58##        H     H                                                                                  ##STR59##                                    5                                                                                  ##STR60##        CH.sub.3                                                                            H                                                                                  ##STR61##                                    6                                                                                  ##STR62##        H     OCH.sub.3                                                                          ##STR63##                                    7                                                                                  ##STR64##        CH.sub.3                                                                            OCH.sub. 3                                                                         ##STR65##                                    8                                                                                  ##STR66##        CH.sub.3                                                                            CH.sub.3                                                                           ##STR67##                                    9                                                                                  ##STR68##        OCH.sub.3                                                                           OCH.sub.3                                                                          ##STR69##                                   10                                                                                  ##STR70##        NHCOCH.sub.3                                                                        H                                                                                  ##STR71##                                   11                                                                                  ##STR72##        NHCOCH.sub.3                                                                        OCH.sub.3                                                                          ##STR73##                                   12                                                                                  ##STR74##        NHCONH.sub.2                                                                        H                                                                                  ##STR75##                                   13                                                                                  ##STR76##        Cl    H                                                                                  ##STR77##                                   14                                                                                  ##STR78##        H     SO.sub.3 H                                                                         ##STR79##                                   15                                                                                  ##STR80##        H     H                                                                                  ##STR81##                                   16                                                                                  ##STR82##        CH.sub.3                                                                            H                                                                                  ##STR83##                                   17                                                                                  ##STR84##        H     OCH.sub.3                                                                          ##STR85##                                   18                                                                                  ##STR86##        CH.sub.3                                                                            H                                                                                  ##STR87##                                   19                                                                                  ##STR88##        H     OCH.sub.3                                                                          ##STR89##                                   20                                                                                  ##STR90##        CH.sub.3                                                                            OCH.sub.3                                                                          ##STR91##                                   21                                                                                  ##STR92##        CH.sub.3                                                                            H                                                                                  ##STR93##                                   22                                                                                  ##STR94##        NHCOCH.sub.3                                                                        H                                                                                  ##STR95##                                   23                                                                                  ##STR96##        CH.sub.3                                                                            H                                                                                  ##STR97##                                   24                                                                                  ##STR98##        NHCONH.sub.2                                                                        H                                                                                  ##STR99##                                   25                                                                                  ##STR100##       CH.sub.3                                                                            H                                                                                  ##STR101##                                  26                                                                                  ##STR102##       CH.sub.3                                                                            OCH.sub.3                                                                          ##STR103##                                  27                                                                                  ##STR104##       CH.sub.3                                                                            H                                                                                  ##STR105##                                  28                                                                                  ##STR106##       CH.sub.3                                                                            H                                                                                  ##STR107##                                  29                                                                                  ##STR108##       H     H                                                                                  ##STR109##                                  30                                                                                  ##STR110##       H     OCH.sub.3                                                                          ##STR111##                                  31                                                                                  ##STR112##       H     H                                                                                  ##STR113##                                  32                                                                                  ##STR114##       CH.sub.3                                                                            H                                                                                  ##STR115##                                  33                                                                                  ##STR116##       CH.sub.3                                                                            OCH.sub.3                                                                          ##STR117##                                  34                                                                                  ##STR118##       H     OCH.sub.3                                                                          ##STR119##                                  35                                                                                  ##STR120##       H     OCH.sub.3                                                                          ##STR121##                                  36                                                                                  ##STR122##       CH.sub.3                                                                            H                                                                                  ##STR123##                                  37                                                                                  ##STR124##       H     H                                                                                  ##STR125##                                  38                                                                                  ##STR126##       CH.sub.3                                                                            H                                                                                  ##STR127##                                  39                                                                                  ##STR128##       H     H                                                                                  ##STR129##                                  40                                                                                  ##STR130##       CH.sub.3                                                                            H                                                                                  ##STR131##                                  41                                                                                  ##STR132##       H     OCH.sub.3                                                                          ##STR133##                                  42                                                                                  ##STR134##       H     H                                                                                  ##STR135##                                  43                                                                                  ##STR136##       CH.sub.3                                                                            H                                                                                  ##STR137##                                  44                                                                                  ##STR138##       CH.sub.3                                                                            OCH.sub.3                                                                          ##STR139##                                  45                                                                                  ##STR140##       H     OCH.sub.3                                                                          ##STR141##                                  46                                                                                  ##STR142##       CH.sub.3                                                                            CH.sub.3                                                                           ##STR143##                                  47                                                                                  ##STR144##       NHCOCH.sub.3                                                                        H                                                                                  ##STR145##                                  48                                                                                  ##STR146##       H     H                                                                                  ##STR147##                                  49                                                                                  ##STR148##       H     OCH.sub.3                                                                          ##STR149##                                  50                                                                                  ##STR150##       H     H                                                                                  ##STR151##                                  51                                                                                  ##STR152##       H     OCH.sub.3                                                                          ##STR153##                                  52                                                                                  ##STR154##       CH.sub.3                                                                            OCH.sub.3                                                                          ##STR155##                                  53                                                                                  ##STR156##       CH.sub.3                                                                            H                                                                                  ##STR157##                                  54                                                                                  ##STR158##       H     H                                                                                  ##STR159##                                  55                                                                                  ##STR160##       CH.sub.3                                                                            H                                                                                  ##STR161##                                  56                                                                                  ##STR162##       CH.sub.3                                                                            OCH.sub.3                                                                          ##STR163##                                  57                                                                                  ##STR164##       H     OCH.sub.3                                                                          ##STR165##                                  58                                                                                  ##STR166##       H     H                                                                                  ##STR167##                                  59                                                                                  ##STR168##       CH.sub.3                                                                            OCH.sub.3                                                                          ##STR169##                                  60                                                                                  ##STR170##       NHCOCH.sub.3                                                                        H                                                                                  ##STR171##                                  61                                                                                  ##STR172##       H     H                                                                                  ##STR173##                                  62                                                                                  ##STR174##       CH.sub.3                                                                            H                                                                                  ##STR175##                                  63                                                                                  ##STR176##       H     H                                                                                  ##STR177##                                  64                                                                                  ##STR178##       H     OCH.sub.3                                                                          ##STR179##                                  65                                                                                  ##STR180##       H     H                                                                                  ##STR181##                                  66                                                                                  ##STR182##       H     OCH.sub.3                                                                          ##STR183##                                  67                                                                                  ##STR184##       H     H                                                                                  ##STR185##                                  68                                                                                  ##STR186##       CH.sub.3                                                                            H                                                                                  ##STR187##                                  69                                                                                  ##STR188##       H     OCH.sub.3                                                                          ##STR189##                                  70                                                                                  ##STR190##       H     H                                                                                  ##STR191##                                  71                                                                                  ##STR192##       H     OCH.sub.3                                                                          ##STR193##                                  72                                                                                  ##STR194##       H     H                                                                                  ##STR195##                                  73                                                                                  ##STR196##       CH.sub.3                                                                            OCH.sub.3                                                                          ##STR197##                                  74                                                                                  ##STR198##       CH.sub.3                                                                            H                                                                                  ##STR199##                                  75                                                                                  ##STR200##       H     H                                                                                  ##STR201##                                  76                                                                                  ##STR202##       H     H                                                                                  ##STR203##                                  77                                                                                  ##STR204##       CH.sub.3                                                                            H                                                                                  ##STR205##                                  78                                                                                  ##STR206##       H     H                                                                                  ##STR207##                                  79                                                                                  ##STR208##       CH.sub.3                                                                            H                                                                                  ##STR209##                                  80                                                                                  ##STR210##       H     OCH.sub.3                                                                          ##STR211##                                  81                                                                                  ##STR212##       H     H                                                                                  ##STR213##                                  82                                                                                  ##STR214##       CH.sub.3                                                                            H                                                                                  ##STR215##                                  83                                                                                  ##STR216##       H     H                                                                                  ##STR217##                                  84                                                                                  ##STR218##       H     OCH.sub.3                                                                          ##STR219##                                  85                                                                                  ##STR220##       CH.sub.3                                                                            H                                                                                  ##STR221##                                  86                                                                                  ##STR222##       NHCOCH.sub.3                                                                        H                                                                                  ##STR223##                                  87                                                                                  ##STR224##       CH.sub.3                                                                            H                                                                                  ##STR225##                                  88                                                                                  ##STR226##       H     H                                                                                  ##STR227##                                  89                                                                                  ##STR228##       CH.sub.3                                                                            H                                                                                  ##STR229##                                  90                                                                                  ##STR230##       H     H                                                                                  ##STR231##                                  91                                                                                  ##STR232##       H     OCH.sub.3                                                                          ##STR233##                                  92                                                                                  ##STR234##       CH.sub.3                                                                            H                                                                                  ##STR235##                                  93                                                                                  ##STR236##       NHCOCH.sub.3                                                                        H                                                                                  ##STR237##                                  94                                                                                  ##STR238##       H     H                                                                                  ##STR239##                                  95                                                                                  ##STR240##       CH.sub.3                                                                            H                                                                                  ##STR241##                                  96                                                                                  ##STR242##       H     OCH.sub.3                                                                          ##STR243##                                  97                                                                                  ##STR244##       H     H                                                                                  ##STR245##                                  98                                                                                  ##STR246##       H     H                                                                                  ##STR247##                                  99                                                                                  ##STR248##       H     H                                                                                  ##STR249##                                  100                                                                                 ##STR250##       H     OCH.sub.3                                                                          ##STR251##                                  101                                                                                 ##STR252##       H     H                                                                                  ##STR253##                                  102                                                                                 ##STR254##       H     H                                                                                  ##STR255##                                  103                                                                                 ##STR256##       H     H                                                                                  ##STR257##                                  104                                                                                 ##STR258##       H     OCH.sub.3                                                                          ##STR259##                                  105                                                                                 ##STR260##       CH.sub.3                                                                            H                                                                                  ##STR261##                                  106                                                                                 ##STR262##       H     H                                                                                  ##STR263##                                  107                                                                                 ##STR264##       CH.sub.3                                                                            OCH.sub.3                                                                          ##STR265##                                  108                                                                                 ##STR266##       NHCOCH.sub.3                                                                        H                                                                                  ##STR267##                                  109                                                                                 ##STR268##       H     OCH.sub.3                                                                          ##STR269##                                  110                                                                                 ##STR270##       H     H                                                                                  ##STR271##                                  111                                                                                 ##STR272##       H     H                                                                                  ##STR273##                                  112                                                                                 ##STR274##       H     H                                                                                  ##STR275##                                  __________________________________________________________________________

EXAMPLES 113 TO 128/Table 2

By a method analogous to that of Examples 2 and 3 further compounds offormula I may be prepared using appropriate starting compounds. Theycorrespond to formula (B) ##STR276## in which the symbols are defined inTable 2 below. In the last column of Table 2 the shade of the paperdyeing obtained with each of the listed dyestuffs is indicated, whereby

a is greenish-yellow,

b is neutral-yellow, and

c is weakly reddish yellow.

These paper dyeings show good light and wet fastness properties.

                  TABLE 2                                                         ______________________________________                                        Compounds of formula (B)                                                           SO.sub.3 H                                                                    on the                                                                        naphthyl                                                                      ring                                shade                                Ex.  in the                              on                                   No.  positions                                                                              R.sub.2     R.sub.3x                                                                            Y.sub.2  paper                                ______________________________________                                        113  6,8      CH.sub.3    H     ═NCN b                                    114  "        "           CH.sub.3                                                                            "        b                                    115  "        "           OCH.sub.3                                                                           "        c                                    116  "        --NHCOCH.sub.3                                                                            H     "        c                                    117  "        --NHCONH.sub.2                                                                            H     "        c                                    118  5,7      H           H     "        a                                    119  "        CH.sub.3    H     "        b                                    120  "        H           OCH.sub.3                                                                           "        b                                    121  "        --NHCOCH.sub.3                                                                            H     "        c                                    122  4,8      H           OCH.sub.3                                                                           "        b                                    123  6,8      H           H     ═NCONH.sub.2                                                                       a                                    124  "        H           OCH.sub.3                                                                           "        b                                    125  "        CH.sub.3    H     "        b                                    126  5,7      H           H     "        a                                    127  "        H           OCH.sub.3                                                                           "        b                                    128  4,8      H           H     "        b                                    ______________________________________                                    

EXAMPLE 129

20 Parts of 3-nitrobenzoyl chloride are reacted with 42 parts of theaminoazo dyestuff prepared by coupling of diazotised2-aminonaphthalene-4,8-disulphonic acid with m-toluidine. Subsequently,the resulting product is reduced with sodium sulphide. Diazotisation iseffected in accordance with conventional manner and the diazo product iscoupled with 2.5 parts of 4-methyl-6-hydroxypyridone-(2). The resultingdyestuff corresponds to the formula ##STR277## it dyes paper a brilliantneutral-yellow shade. The paper dyeings show good light and wet fastnessproperties.

EXAMPLES 130 TO 148/Table 3

By a method analogous to that described in Example 129 further compoundsof formula I may be prepared which are listed in the following Table 3.They correspond to formula (C) ##STR278## in which the symbols aredefined in Table 3 below. These dyestuffs dye paper a greenish-yellow toneutral-yellow shade, the resulting paper dyeings show good generalfastness properties.

                                      TABLE 3                                     __________________________________________________________________________    Compounds of formula (C)                                                      Ex. No.                                                                            D               R.sub.2                                                                             R.sub.3x                                                                          K                                              __________________________________________________________________________    130                                                                                 ##STR279##     H     H                                                                                  ##STR280##                                    131  "               NHCOCH.sub.3                                                                        H   "                                              132  "               H     OCH.sub.3                                                                         "                                              133  "               CH.sub.3                                                                            "   "                                              134                                                                                 ##STR281##     H     H   "                                              135  "               CH.sub.3                                                                            H   "                                              136  "               H     OCH.sub.3                                                                         "                                              137                                                                                 ##STR282##     H     H   "                                              138  "               CH.sub.3                                                                            H   "                                              139  "               H     OCH.sub.3                                                                         "                                              140                                                                                 ##STR283##     H     "   "                                              141                                                                                 ##STR284##     CH.sub.3                                                                            H   "                                              142                                                                                 ##STR285##     "     H   "                                              143  "               "     H                                                                                  ##STR286##                                    144                                                                                 ##STR287##     "     H   "                                              145                                                                                 ##STR288##     CH.sub.3                                                                            H                                                                                  ##STR289##                                    146  "               H     OCH.sub.3                                                                          ##STR290##                                    147  "               CH.sub.3                                                                            H                                                                                  ##STR291##                                    148                                                                                 ##STR292##     "     H   "                                              __________________________________________________________________________

EXAMPLE 149

42 Parts of the aminoazo dyestuff prepared by coupling of diazotised2-aminonaphthalene-4,8-disulphonic acid with m-toluidine are reactedwith 25 parts of acetamidobenzene-4-sulphonyl chloride. Subsequently,alkaline saponification is effected. The thus obtained product isdiazotised in accordance with conventional methods and coupled with 2.5parts of 4-methyl-6-hydroxypyridone-(2). The dyestuff corresponding tothe formula ##STR293## is obtained which dyes paper a neutral-yellowshade. The light and wet fastness properties of these paper dyeings aregood.

EXAMPLE 150

When according to the method described in Example 149, 40.7 parts of theaminoazo dyestuff prepared by coupling of diazotised2-aminonaphthalene-4,8-disulphonic acid with aniline-ω-methanesulphonicacid and subsequent alkaline saponification are used the dyestuffcorresponding to the formula ##STR294## is obtained which dyes paper aneutral-yellow shade resulting in paper dyeings of good light and wetfastness properties.

EXAMPLE 151

40.7 Parts of 2-(4'-aminobenzeneazo)naphthalene-4,8-disulphonic acid aresuspended in 400 parts of ice water. To this suspension 18.5 parts ofcyanuric chloride are added. Stirring is effected for three hours at0°-5°, whereby the pH is kept at 5-6 by adding sodium hydroxidesolution. After two hours the condensation is completed. Then, 14 partsof 3-nitroaniline are added, and the mixture is slowly heated to 80°,the pH is kept at 6-7. After a further six hours the starting materialis no longer detectable. To the resulting dyestuff suspension 40 partsof sodium sulphide are added slowly, whereby the reduction of the nitrogroup commences. After the reduction is completed, the mixture is cooledto room temperature, whilst stirring. The thus obtained compoundcorresponding to the formula ##STR295## is filtered and stirred into 200parts of water. To this mixture 20 parts of conc. hydrochloric acid areadded followed by 25 parts of a 4N sodium nitrite solution, which areadded dropwise. Stirring is effected for three hours. After the additionof 13 parts of 4-methyl-6-hydroxypyridone-(2) the pH is adjusted to 8-9by adding sodium hydroxide solution. A yellow dyestuff is obtained whichis filtered, washed with brine and dried. The dyestuff corresponding tothe formula ##STR296## dyes paper a neutral-yellow shade. The resultingpaper dyeings have good light and wet fastness properties.

EXAMPLES 152 TO 160/Table 4

By a method analogous to that described in Example 151 further compoundsof formula I may be prepared which are listed in the following Table 4.The chlorine atom bound to the triazine ring may be replaced preferablyby an amine such as mono- or di-ethanolamine in accordance with knownmethods. The compounds correspond to formula (E) ##STR297## in which thesymbols are defined in Table 4 below. These dyestuffs dye paper aneutral-yellow shade, the resulting paper dyeings show good light andwet fastness properties.

                                      TABLE 4                                     __________________________________________________________________________    Compounds of formula (E)                                                      Ex. No.                                                                            D            R.sub.2                                                                          R.sub.3                                                                           Y          Q.sub.2                                                                              Q.sub.3                            __________________________________________________________________________    152                                                                                 ##STR298##  H  H   Cl                                                                                        ##STR299##                                                                          H                                  153  "            H  H   N(CH.sub.2 CH.sub.2 OH).sub.2                                                            "      H                                  154  "            H  OCH.sub.3                                                                         "          H      H                                  155  "            CH.sub.3                                                                         "   NHCH.sub.2 CH.sub.2 OH                                                                   CONH.sub.2                                                                           H                                  156  "            H  H   NHCH.sub.2 CH.sub.2 SO.sub.3 H                                                           H      H                                  157  "            CH.sub.3                                                                         H   "          H      C.sub.2 H.sub.5                    158                                                                                 ##STR300##  H  H   Cl         H      "                                  159  "            H  H   NHCH.sub.2 CH.sub.2 OH                                                                   H      "                                  160  "            CH.sub.3                                                                         H   "          H      H                                  __________________________________________________________________________

In accordance with the reaction and isolation conditions as describedthe compounds of Examples 1 to 160 are obtained in sodium salt formprovided that no internal salt is formed. They may, depending on thereaction and isolation conditions, or by reacting the sodium salts inaccordance with known methods also be obtained in free acid form or inother salt forms, for example those salt forms or mixed salt formscontaining one or more cations indicated in the description above.

EXAMPLE 161

The dyestuff prepared according to the method given in Example 2 isstirred into 200 parts of water prior to drying, and is mixed with 20parts of 30% hydrochloric acid. After having been stirred for a longertime, the dyestuff, in free acid form, is filtered off and is added into15 parts of triethanolamine. The dyestuff dissolves whilst releasingheat. This solution is adjusted to 90 parts by adding water to give adyestuff solution which is storage-stable and ready for use.

EXAMPLE 162

If in Example 161 lithium hydroxide solution is used instead oftriethanolamine, a liquid aqueous dye preparation is obtained whichcontains the dyestuff according to Example 2 in lithium salt form.

By a method analogous to that described in Example 161 or 162 thedyestuffs of Examples 1 and 3 to 160 may also be converted into liquidaqueous dyeing preparations showing high stability on storage.

In the following examples the application of the compounds of thisinvention as well as of liquid aqueous dyeing preparations thereof isillustrated.

APPLICATION EXAMPLE A

70 Parts of chemically bleached sulphite cellulose obtained frompinewood and 30 parts of chemically bleached sulphite cellulose obtainedfrom birchwood are ground in a hollander in 2000 parts of water. 0.2Part of the dyestuff of Example 1 or 2 are sprinkled into this pulp or1.0 part of the liquid dyestuff preparation according to Example 161 or162 are added to this pulp. After mixing for 20 minutes, paper isproduced from this pulp. The absorbent paper obtained in this way isdyed a neutral-yellow shade. The waste water is practically colourless.

APPLICATION EXAMPLE B

0.5 Part of the dyestuff of Example 1 or 2 are dissolved in 100 parts ofhot water and cooled to room temperature. This solution is added to 100parts of chemically bleached sulphite cellulose which have been groundin a hollander with 2000 parts of water. After thorough mixing for 15minutes, sizing takes place in the usual way with rosin size andaluminum sulphate. Paper which is produced from this material is ofneutral-yellow shade and has good waste water and wet fastnessproperties.

APPLICATION EXAMPLE C

An absorbent length of unsized paper is drawn at 40°-50° through adyestuff solution having the following composition:

0.5 part of the dyestuff of Example 1 or 2 or of the liquid dyepreparation according to Example 161 or 162,

0.5 part of starch, and

99.0 parts of water.

The excess dyestuff solution is squeezed out through two rollers. Thedried length of paper is dyed a neutral-yellow shade.

The dyestuffs or liquid dyestuff preparations of the remaining examplesmay also be used for dyeing paper according to Application Examples A toC. The resulting paper dyeings are dyed a yellow shade. They have goodgeneral fastness properties.

Application Example D (leather)

100 Parts of intermediately dried chrome velours leather are agitatedfor one hour at 50° in a vessel with a liquor consisting of 400 parts ofwater, 2 parts of 25% ammonium hydroxide solution and 0.2 part of aconventional wetting agent. Then the liquor is run off. To the agitatedstill wet chrome velours leather 400 parts of water of 60° and 1 part of25% ammonium hydroxide solution are added. After the addition of 5 partsof the dyestuff of Example 2 dissolved in 200 parts of water, dyeing iseffected during 90 minutes at 60°. Subsequently, 50 parts of 8% formicacid are slowly added to adjust to an acidic pH, and agitating iscontinued for a further 30 minutes. The leather is then rinsed, driedand prepared in the normal way giving a leather evenly dyed in a yellowtone with good light fastness properties.

APPLICATION EXAMPLE E (cotton)

To a dyebath consisting of 3000 parts of demineralised water, 2 parts ofsodium carbonate and 1 part of the dyestuff of Example 2, 100 parts ofpre-wetted cotton fabric are added at 30°. After the addition of 10parts of sodium sulphate, the dyebath is heated to the boil within 30minutes whereby, at a temperature of 50° and 70°, at each of thesestages a further 10 parts of sodium sulphate are added. Dyeing iscontinued for a further 15 minutes at the boil followed by the additionof a further 10 parts of sodium sulphate. The dyebath is then cooleddown. At 50° the dyed fabric is removed from the dye liquor, rinsed withwater and dried at 60°. A neutral-yellow cotton dyeing is obtainedhaving good light and wet fastness properties.

APPLICATION EXAMPLE F (polyamide)

0.1 Part of the dyestuff of Example 2 are dissolved in 300 part ofwater, and 0.2 part of ammonium sulphate are added to this solution.Then the pre-wetted textile fabric (5 parts wool gaberdine or 5 partsnylon satin) is entered into the bath which is heated to the boil duringthe course of 30 minutes. The water that evaporates during the dyeingprocess for 30 minutes is replaced, and dyeing at the boil is continuedfor a further 30 minutes. Finally, the dyed fabric is removed from theliquor and rinsed with water. After drying a neutral-yellow polyamidedyeing is obtained having good light and wet fastness properties.

In analogous manner as described in Application Examples D to F thedyestuffs of the remaining examples may be used for dyeing. The thusobtained substrates are dyed a yellow tone and have good fastnessproperties.

What is claimed is:
 1. A compound of the formula ##STR301## or a saltthereof, wherein Da is ##STR302## wherein R₆ is hydrogen or sulfo,R₇ ishydrogen, halo, C₁₋₄ alkyl, C₁₋₄ alkoxy or (C₁₋₄ alkyl)carbonylamino, xis 0 or 1, and y is 1 or 2, Kb is ##STR303## wherein Q_(1a) is hydrogen;cyano; amino; hydroxy; methyl; ethyl; 2-hydroxyethyl; 2-(C₁₋₂alkoxy)ethyl; methoxy; ethoxy; cyclohexyl; phenyl; phenyl substituted by1 or 2 substituents selected from methyl, methoxy, chloro, carboxy andsulfo; phenyl(C₁₋₂ alkyl); phenyl(C₁₋₂ alkyl) the phenyl group of whichis substituted by 1 or 2 substituents selected from methyl, methoxy,chloro, carboxy and sulfo; pyridiniummethyl; --CO--R_(10a) or--(CH₂)_(r) --R_(11a), whereinR_(10a) is hydroxy, amino, methoxy orethoxy, R_(11a) is cyano, chloro, sulfo, --O--SO₃ H, pyridyl or--CO--R_(12a), wherein R_(12a) is hydroxy, amino, methyl, ethyl, methoxyor ethoxy, and Q_(2a) is hydrogen; cyano; chloro; sulfo; --NR_(13b)R_(14b) ; methyl; ethyl; C₁₋₂ alkyl monosubstituted by hydroxy, phenyl,sulfo or --O--SO₃ H; --CO--R_(15a) ; --CH₂ --NHCO--R_(16a) --E_(1b) ;pyridinium; pyrimidinium,; benzoimidazolium; or pyridinium, pyrimidiniumor benzoimidazolium monosubstituted by methyl, amino, methylamino ordimethylamino, whereinE_(1b) is hydrogen, chloro, --NR_(23a) R_(24a),--N.sup.⊕ R_(25a) R_(26a) R_(27a) or sulfo, each of R_(13b) and R_(14b)is independently hydrogen, methyl or --CO--R_(16a) --E_(1b), whereinE_(1b) is as defined above, and R_(15a) is hydroxy, amino methylamino,dimethylamino, methyl, ethyl, methoxy or ethoxy, or Q_(1a) and Q_(2a)taken together are --CH₂ --Y₃ --CH₂ --, wherein Y₃ is --(CH₂)_(r) --,##STR304## and the * denotes the carbon atom attached to the --CH₂ --radical in the Q_(1a) -position, Q_(3a) is hydrogen; --NR_(18a) R_(19a); phenyl; phenyl(C₁₋₂ alkyl); cyclohexyl; C₁₋₄ alkyl; C₁₋₄ alkylmonosubstituted by hydroxy, cyano, C₁₋₂ alkoxy, --CO--R_(20a), sulfo or--O--SO₃ H; --R_(16b) --E_(2a) ; ##STR305## wherein E_(2a) is --NR₂₃R₂₄, --NR.sup.⊕ R₂₅ R₂₆ R₂₇ ##STR306## wherein each R_(22a) isindependently chloro or --N(R₃₀)₂,R_(16b) is linear or branched C₁₋₃alkylene, each of R_(18a) and R_(19a) is independently hydrogen, methyl,ethyl or phenyl, R_(20a) is hydroxy, methoxy or ethoxy, and R_(21a) is--NR₂₃ R₂₄, --N.sup.⊕ R₂₅ R₂₆ R₂₇, --NHCO--R_(16a) --NR₂₃ R₂₄,--NHCO--R_(16a) --N.sup.⊕ R₂₅ R₂₆ R₂₇, --SO₂ NH--R_(16a) --NR₂₃ R₂₄,--SO₂ NH--R_(16a) --N.sup.⊕ R₂₅ R₂₆ R₂₇, --CONH--R_(16a) --NR₂₃ R₂₄ or--CONH--R_(16a) --N.sup.⊕ R₂₅ R₂₆ R₂₇, Q₄ is hydrogen or hydroxy, withthe proviso that Q₄ is hydrogen when Q_(1a) is hydroxy, R_(8b) ismethyl, carboxy or --CONH₂, R_(9a) is hydrogen, methyl, phenyl or phenylsubstituted by 1 or 2 substituents selected from C₁₋₄ alkyl, C₁₋₄alkoxy, chloro, acetamido, --NHCO--R₁₆ --NR₂₃ R₂₄, --NHCO--R₁₆ --N.sup.⊕R₂₅ R₂₆ R₂₇, --SO₂ NH--R₁₆ --NR₂₃ R₂₄, --SO₂ NH--R₁₆ --N.sup.⊕ R₂₅ R₂₆R₂₇, carboxy and sulfo, wherein R₁₆ is linear or branched C₁₋₆ alkylene,Y₁ is hydroxy or amino, and Y_(2a) is ═O, ═S, ═NH, ═NCN or ═NCONH₂,R_(1x) is hydrogen, C₁₋₄ alkyl or C₁₋₄ alkyl monosubstituted by hydroxy,chloro, cyano, carboxy or sulfo, each of R_(2x) and R_(3x) isindependently hydrogen, halo, C₁₋₄ alkyl, sulfo(C₁₋₄ alkyl), --(CH₂)_(t)--NR_(23a) R_(24a), --(CH₂)_(t) --N.sup.⊕ R_(25a) R_(26a) R_(27a), C₁₋₄alkoxy, sulfo(C₁₋₄ alkoxy), --NHCO--R_(5x), --NR_(23a) R_(24a),--N.sup.⊕ R_(25a) R_(26a) R_(27a) or sulfo, wherein R_(5x) is C₁₋₄alkyl, --(CH₂)_(t) --NR_(23a) R_(24a), --(CH₂)_(t) --N.sup.⊕ R_(25a)R_(26a) R_(27a), C₁₋₄ alkoxy or amino, with the proviso that R_(2x) isother than sulfo, R_(4x) is hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, halo,nitro or sulfo, and Xa is --CO--, --CH₂ --, --SO₂ --, --CONR_(1x) -- or##STR307## wherein Y_(x) is hydroxy, C₁₋₄ alkoxy, phenoxy, amino, C₁₋₂alkylamino, C₂₋₄ hydroxyalkylamino, N,N-di-(C₂₋₄ hydroxyalkyl)amino,--NH--(CH₂)_(m) --SO₃ H, anilino, morpholino, piperidino, piperazino orN-methylpiperazino, wherein m is 2 or 3, andR_(1x) is as definedabove,wherein each R_(1b) is independently hydrogen, methyl or ethyl,each R_(16a) is independently C₁₋₂ alkylene, each R₂₃ and R₂₄ isindependently hydrogen, C₁₋₂ alkyl, n-C₂₋₃ hydroxyalkyl or benzyl, or--NR₂₃ R₂₄ is pyrrolidino, piperidino, morpholino, piperazino orN-methylpiperazino, each R_(23a) and R_(24a) is independently hydrogen,methyl or ethyl, or --NR_(23a) R_(24a) is piperidino, morpholino,piperazino or N-methylpiperazino, each R₂₅ and R₂₆ is independently C₁₋₂alkyl, n-C₂₋₃ hydroxyalkyl or benzyl, and each R₂₇ is independentlymethyl, ethyl or benzyl, or --N.sup.⊕ R₂₅ R₂₆ R₂₇ is pyridinium,pyridinium monosubstituted or disubtituted by methyl or ##STR308##wherein Z is a direct bond, --CH₂ --, --O--, --NH-- or --N(CH₃)--,andR₂₇ is as defined above, each R_(25a), R_(26a) and R_(27a) isindependently methyl or ethyl, or --N.sup.⊕ R_(25a) R_(26a) R_(27a) ispyridinium, pyridinium monosubstituted or disubstituted by methyl or##STR309## wherein Z' is --CH₂ --, --O--, --NH-- or --N(CH₃)--,andR_(27a) is as defined above, each R₃₀ is independently hydrogen, C₁₋₂alkyl or C₁₋₂ alkyl monosubstituted by hydroxy, cyano or C₁₋₂ alkoxy,each r is independently 1 or 2, each t is independently 1, 2 or 3, andeach halo is independently fluoro, chloro or bromo,with the provisosthat the compound contains 1, 2, 3 or 4 sulfo groups, the total numberof sulfo and carboxy groups equals or exceeds the total number of basicand cationic groups, and the positive charge of each cationic groupindependently is balanced by the negative charge of an --SO₃.sup.⊖ or--COO.sup.⊖ group of the molecule or of a non-chromophoric anion, or amixture of such compounds each of which is in free acid or salt form. 2.A compound according to claim 1, or a salt thereof.
 3. A compoundaccording to claim 2, or a salt thereof, wherein Xa is --CO--, --CH₂ --,--CO--NR_(1a) -- or ##STR310## wherein R_(1a) is hydrogen, methyl, ethylor C₁₋₃ alkyl monosubstituted by hydroxy, chloro, cyano, carboxy orsulfo, andY_(ax) is hydroxy, methoxy, amino, C₁₋₂ -alkylamino, C₂₋₄hydroxyalkylamino, N,N-di-(C₂₋₄ hydroxyalkyl)amino, --NH--(CH₂)_(m)--SO₃ H, anilino, morpholino, piperidino, piperazino orN-methylpiperazino, wherein m is 2 or
 3. 4. A compound according toclaim 2, or a salt thereof, wherein Xa is --CO--, --SO₂ -- or ##STR311##wherein Y_(ax) is hydroxy, methoxy, amino, C₁₋₂ alkylamino, C₂₋₄hydroxyalkylamino, N,N-di-(C₂₋₄ hydroxyalkyl)amino, --NH--(CH₂)_(m)--SO₃ H, anilino, morpholino, piperidino, piperazino orN-methylpiperazino, wherein m is 2 or
 3. 5. A compound according toclaim 2, or a salt thereof, wherein each R_(1x) is independentlyhydrogen, methyl, ethyl or C₁₋₃ alkyl monosubstituted by hydroxy,chloro, cyano, carboxy or sulfo.
 6. A compound according to claim 2, ora salt thereof, whereinR_(2x) is in the 6-position of Ring A, and R_(3x)is in the 3-position of Ring A.
 7. A compound according to claim 6, or asalt thereof, whereinR_(2x) is hydrogen, methyl, methoxy, acetamido or--NHCONH₂, and R_(3x) is hydrogen, methyl or methoxy.
 8. A compoundaccording to claim 2, or a salt thereof, wherein the Kb--N═N-- group isin the 3- or 4-position of Ring B.
 9. A compound according to claim 2,or a salt thereof, wherein Da is 4,8-disulfonaphthyl-2,6,8-disulfonaphthyl-2 or ##STR312## wherein R_(7b) is hydrogen, methylor methoxy, and Xa is --CO-- or ##STR313## wherein Y_(ax) is hydroxy,methoxy, amino, C₁₋₂ -alkylamino, C₂₋₄ hydroxyalkylamino, N,N-di(C₂₋₄hydroxyalkyl)amino, --NH--(CH₂)_(m) --SO₃ H, anilino, morpholino,piperidino, piperazino, or N-methylpiperazino, wherein m is 2 or
 3. 10.A compound according to claim 1, or a salt thereof, wherein Kb is##STR314## or a mixture of such compounds each of which is in free acidor salt form.
 11. A compound according to claim 1, or a salt thereof.12. A compound according to claim 11, or a salt thereof, wherein theKb--N═N-- group is in the 3- or 4-position of Ring B.
 13. A compoundaccording to claim 12, or a salt thereof, wherein Xa is --CO--, --CH₂--, --CONR_(1a) -- or ##STR315## wherein R_(1a) is hydrogen, methyl,ethyl or C₁₋₃ alkyl monosubstituted by hydroxy, chloro, cyano, carboxyor sulfo, and Y_(ax) is hydroxy, methoxy, amino, C₁₋₂ -alkylamino, C₂₋₄hydroxyalkylamino, N,N-di-(C₂₋₄ hydroxyalkyl)amino, --NH (CH₂)_(m) --SO₃H, anilino, morpholino, piperidino, piperazino or N-methylpiperazino,wherein m is 2 or
 3. 14. A compound according to claim 11, or a saltthereof, whereineach R_(1x) is independently hydrogen, methyl, ethyl orC₁₋₃ alkyl monosubstituted by hydroxy, chloro, cyano, carboxy or sulfo,R_(2x) is hydrogen, chloro, methyl, methoxy, --NHCO--R_(5a), --(CH₂)_(t)--SO₃ H, --O--(CH₂)₃ --SO₃ H, --(CH₂)_(t) --NR_(23a) R₂₄ a or--(CH₂)_(t) --N.sup.⊕ R_(25a) R_(26a) R₂₇ a, wherein R_(5a) is methyl,methoxy, amino, --(CH₂)_(t) --NR_(23a) R_(24a) or --(CH₂)_(t) --N.sup.⊕R_(25a) R_(26a) R_(27a), R_(3x) is hydrogen, methyl or methoxy, andY_(x) is hydroxy, methoxy, amino, C₁₋₂ alkylamino, C₂₋₄hydroxyalkylamino, N,N-di-(C₂₋₄ hydroxyalkyl)amino, --NH--(CH₂)_(m)--SO₃ H, anilino, morpholino, piperidino, piperazino orN-methylpiperazino.
 15. A compound according to claim 14, or a saltthereof, whereinR_(2x) is in the 6-position of Ring A, and R_(3x) is inthe 3-position of Ring A.
 16. A compound according to claim 14, or asalt thereof, wherein R_(2x) is hydrogn, methyl, methoxy, acetamido or--NHCONH₂.
 17. A compound according to claim 16, or a salt thereof,wherein the Kb--N═N-- group is in the 3- or 4-position of Ring B.
 18. Acompound according to claim 17, or a salt thereof, wherein Kb is##STR316##
 19. A compound according to claim 17, or a salt thereof,wherein Kb is ##STR317##
 20. A compound according to claim 17 having theformula ##STR318## or a salt thereof, wherein R_(2b) is hydrogen,methyl, methoxy, acetamido or --NHCONH₂,R_(3a) is hydrogen, methyl ormethoxy, R_(4ax) is hydrogen, C₁₋₂ alkyl, C₁₋₂ alkoxy or sulfo, andX_(c) is --CO--, --SO₂ -- or ##STR319## wherein Yax is hydroxy, methoxy,amino, C₁₋₂ alkylamino, C₂₋₄ hydroxyalkylamino, N,N-di-(C₂₋₄hydroxyalkyl)amino, --NH--(CH₂)_(m) --SO₃ H, anilino, morpholino,piperidino, piperazino or N-methylpiperazino,with the provisos that thecompound contains 1, 2, 3 or 4 sulfo groups and the number of sulfogroups equals or exceeds the total number of basic and cationic groups.21. A compound according to claim 20, or a salt thereof, wherein Xc is##STR320##
 22. A compound according to claim 20, or a salt thereof,wherein Da is 1,5-, 3,6-, 4,8-, 5,7- or 6,8-disulfonaphthyl-2, 3,6,8- or4,6,8-trisulfonaphthyl-2, 3,6-, 4,6-, 3,8- or 4,8-disulfonaphthyl-1,3,6,8-trisulfonaphthyl-1 or ##STR321## wherein R_(7a) is hydrogen,chloro, methyl, methoxy or acetamido.
 23. A compound according to claim20, or a salt thereof, wherein R_(1b) is hydrogen.
 24. A compoundaccording to claim 20, or a salt thereof, wherein R_(4ax) is hydrogen.25. A compound according to claim 20, or a salt thereof, wherein Xc is--CO--.
 26. A compound according to claim 20, or a salt thereof, whereinthe Kb--N═N-- group is in the 4-position of Ring B.
 27. A compoundaccording to claim 26, or a salt thereof, whereinR_(1b) is hydrogen,R_(4ax) is hydrogen, and Xc is --CO--.
 28. A compound according to claim27, or a salt thereof, wherein Kb is ##STR322## wherein Y_(2b) is ═NCNor ═NCONH₂.
 29. The compound according to claim 28 having the formula##STR323## or a salt thereof.
 30. The compound according to claim 29 insodium salt form.
 31. The compound according to claim 28 having theformula ##STR324## or a salt thereof.
 32. A storage-stable, liquidaqueous dyeing preparation containing a compound according to claim 1,in water-soluble salt form.